1. Field of the Invention
This invention relates to the polymerization of olefins. More particularly, this invention relates to a process having catalyst compositions which are useful for polymerizing one or more monomers comprising ethylene to polymers having an intermediate molecular weight distribution and a good balance of physical properties.
2. Description of the Prior Art
It is known that catalysts of the type variously described as coordination, Ziegler, Ziegler-type, or Ziegler-Natta catalysts are useful for the polymerization of olefins under moderate conditions of temperature and pressure. It is also known that the properties of the polymers obtainable by the use of such catalysts, as well as the relative economies of the processes used to prepare the polymers, vary with several factors, including the choice of the particular monomers, catalyst components, polymerization adjuvants, and other polymerization conditions employed.
During the years since Ziegler catalysts were first publicly disclosed, there has been a considerable amount of research conducted on the use of such catalysts; and numerous publications have resulted from that research. These publications have added much to the knowledge of how to make various types of olefin polymers by various types of processes. However, as is apparent from the amount of research on Ziegler catalysis that is still being conducted throughout the world, as well as the number of patents that are still being issued to inventors working in the field of Ziegler catalysis, the means of attaining certain results when polymerizing olefins with Ziegler catalysts are still frequently unpredictable. The fact that this situation exists is sometimes due to the need to obtain a previously-unattainable combination of results; occasionally due to difficulties in obtaining the same results in a commercial-scale apparatus as in a laboratory-scale reactor; and often due to a polymerization parameter's having an effect, or side-effect, in a given type of polymerization process that is different from effects achieved by its use in prior art processes of a different type.
One aspect of Ziegler catalysis in which the need for further research has been found to exist has been in the provision of catalyst compositions suitable for use in a commerically-feasible process for preparing ethylene polymers having a good balance of physical properties and a molecular weight distribution that can be controlled so as to make the polymers formable by whichever forming technique is intended to be employed for producing articles from the polymers, e.g., injection molding or blow molding.
There are, of course, known processes for preparing injection molding resins, as well as known processes for preparing blow molding resins, by polymerizing ethylene with the aid of Ziegler catalysts. However, the known processes typically suffer one or more of the disadvantages of lack of economy, inability to produce polymers having a suitable balance of properties, and/or unreliability in producing such polymers-particularly in commercial-scale operations. Moreover, the different molecular weight distribution requirements of polymers to be formed by different techniques have compounded the problem of finding a family of catalyst compositions suitable for use in a commercially-feasible process wherein the molecular weight distribution can be controlled so as to produce the desired polymers.
U.S. Pat. No. 4,003,712 by Miller teaches a gas-phase fluidized bed system and process which are capable of being scaled up to commercial size and, being solvent-free, would be less expensive than processes which use solvents or liquid diluents. However, Miller's silyl chromate catalyst does not give polymers of the desired molecular weight distribution and good balance of physical properties. His system contains some features which tend to shorten commercial "on-stream" time. He does not teach how to avoid polymer buildup on reactor surfaces, a phenomenon variously referred to as "coating", "fouling", or "sheeting".
What is still needed is a process employing a catalyst which (a) is suitable for use in a gas-phase polymerization process, (b) has sufficient activity to be economically attractive, (c) is capable of yielding polymers having a controlled molecular weight distribution and a good balance of physical properties, (d) does not cause reactor wall fouling, and (e) a gas-phase fluidized bed process which allows the catalyst to perform at its full potential at commercial scale.
British Pat. No. 1,489,410 (Monsanto) teaches gas-phase polymerization processes which, because of their use of supported Ziegler catalysts having a vanadium component and other factors, are commercially attractive processes. However, as taught in the patent, the processes are designed to result in the formation of polymers having the broad molecular weight distributions suitable for blow molding resins, i.e. molecular weight distributions such that their normalized V.sub.30 /V.sub.300 melt viscosity ratios are above 2.3. Moreover, it has been found that these processes, although useful for preparing blow-molding resins of the type employed for househould chemical containers, do not appear to be adaptable to the preparation of blow-molding resins requiring somewhat narrower molecular weight distributions, e.g., liquid food containers, or to the preparation of injection-molding resins requiring still narrower molecular weight distributions.
Attempts to make the processes of the Monsanto patent suitable for the preparation of injection molding resins, as well as more reliable in the preparation of desirable blow molding resins, by combining the teachings of the patents with the teachings of publications that discuss means of narrowing molecular weight distribution have not been successful. For example, polymers having a sufficiently narrow molecular weight distribution have not been obtained when Monsanto's preferred vanadium halides have been replaced with the alkoxy group-containing vanadium compounds which are within the scope of their patent and which U.S. Pat. Nos. 3,457,244 (Fukuda et al.) and 3,655,583 (Yamamoto et al.) teach to result in the production of polymers having narrower molecular weight distributions when unsupported catalyst systems are employed.
British Pat. No. 1,175,593 (Stamicarbon) teaches a process for preparing ethylene/higher alkene/polyunsaturated compound terpolymers by the use of an unsupported vanadium chloride/alkylaluminum halide catalyst system, the activity of which is increased by adding an alcohol or phenol to the vanadium compound and/or the aluminum compound. According to the speculative teachings of the patent, the alcohol may be a polyhydric alcohol in which the -OH groups are not attached to adjacent carbon atoms, but the patent does not mention any particular polyhydric alcohol that might be used or suggest the effect that the inclusion of a polyhydric alcohol might have on molecular weight distribution if the catalyst composition were being used for the preparation of crystallizable ethylene polymers, such as injection molding or blow molding resins, rather than the rubbers of the patent.
U.S. Pat. No. 3,202,645 to Yancey presents a process for polymerizing and copolymerizing alpha mono and di-olefins by catalysts comprising (a) the product of the reaction between a compound of a metal chosen from the group consisting of the metals of Group IIb and IIIb (where the group numbers correspond to the Mendeleev Periodic Table) and hydroxyl groups on the surface of a finely-divided particulate inorganic solid, preferably finely-divided silica or alumina, and (b) a halide-type compound of a Group IVa, V, VIa, VIIa, or period 4 of Group VIII metal. The polymerization or copolymerization reaction can be effected at suitable temperatures within the range of from about -25.degree. C. to about 250.degree. C., and pressures ranging from below atmospheric upwardly to any desired maximum pressure, for example, 30,000 p.s.i.g. or even higher pressures. U.S. Pat. No. 3,718,636 to Stevens et al teaches obtaining polyolefins having a wide distribution of molecular weights through the use of a catalyst comprising an organometallic compound, and a solid complex component obtained by reacting a solid bivalent metal compound with an impregnation agent which consists of an organometallic compound, separating the solid reaction product, and reacting the solid reaction product with a halogenated derivative of a transition metal. Stevens et al teaches in U.S. Pat. No. 3,787,384 another catalyst suitable for use in olefin polymerization and olefin copolymerization which comprises
(a) at least one organometallic compound, and
(b) a solid catalytic component obtained by reacting a support composed of silica, alumina or both silica and alumina with a compound of the formula MR.sub.n X.sub.m-n in which M is aluminum or magnesium, R is a hydrocarbon radical containing 1 to 20 carbon atoms, X is hydrogen or a halogen, m is the valence of M, and n is a whole number not less than 1 nor greater than m, separating the solid product of the reaction, reacting said product with an excess of a halogen-containing transition metal compound, and separating the solid reaction product.
U.S. Pat. No. 3,925,338 to Ort teaches that control of particle size of olefin polymers produced by gas-phase polymerization of at least one olefin using Ziegler-type catalysts deposited on solid supports in a fluidized-solids operation is effected by controlling the particle size of the catalyst support. U.S. Pat. No. 4,232,140 also to Ort discloses the use of trichlorofluoromethane as a promoter in the polymerization and copolymerization of ethylene with supported Ziegler-type vanadium compound/alkylaluminum compound catalysts in the presence of hydrogen. Ort finds that polymer yields with his supported vanadium-based catalysts are too low for commercial viability unless the catalyst is promoted to high yield with the trichlorofluoromethane promoter. The viscosity ratio data in Ort's examples, which may be related to molecular weight distribution, indicate that none of the polymers have narrow molecular weight distribution. Ort does not teach or suggest how to avoid reactor fouling.
U.S. Pat. No. 3,455,974 to Su teaches an organo-soluble fluorine-containing vanadium compound having the formula: ##STR1## wherein R.sub.1 and R.sub.2 are alkoxy groups, ##STR2## wherein R.sub.7 and R.sub.8 are lower alkyl, lower aryl or taken together, lower alkylene groups or R.sub.1 and R.sub.2 are collectively an ,.alpha..omega.-alkylene dioxy group, said compound having from 2 to 40 carbon atoms. Su also teaches a method of making an organo-soluble fluorine containing vanadium compound which comprises contacting and reacting one molar proportion of vanadyl trifluoride with two molar proportions of a compound having the formula: EQU R.sub.4 R.sub.5 R.sub.6 VO
in the presence of an inert aprotic solvent at about ambient temperature wherein R.sub.4, R.sub.5, and R.sub.6 are alkoxy groups or where R.sub.4 and R.sub.5 collectively are an ,.alpha..omega.-alkylene dioxy group.
Although some of the foregoing patents are concerned with the production of polymers having narrow molecular weight distributions, none of the prior art teaches or suggests an economical, gas-phase, fluidized bed process and catalyst for commercially producing ethylene polymers of controlled molecular weight distribution in combination with a good balance of physical properties.